Silver(I)-Mediated Modification, Dimerization, and Polymerization of an

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Silver(I)-Mediated Modification, Dimerization and Polymerization of an Open-Cage Fullerene Amineh Aghabali, Sharon Jun, Marilyn M. Olmstead, and Alan L. Balch J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b10394 • Publication Date (Web): 21 Nov 2016 Downloaded from http://pubs.acs.org on November 21, 2016

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Silver(I)-Mediated Modification, Dimerization and Polymerization of an Open-Cage Fullerene Amineh Aghabali, Sharon Jun, Marilyn M. Olmstead* and Alan L. Balch* Department of Chemistry, University of California at Davis, One Shields Avenue, Davis, CA 95616, USA Supporting Information Placeholder ABSTRACT: The reactions of the open cage fullerene, MMK-9, with an open 12-membered ring on its surface and silver(I) salts have been examined. The structure of MMK-9 itself has been determined by single crystal X-ray diffraction. MMK-9 reacts with silver trifluoroacetate in air to form the dimer, {MMK-9(OCH3)5Ag(AgO2CCF3)}2. Remarkably, five MeO groups have added to the surface of the open cage in a pattern that surrounds a pentagon immediately adjacent to the opening in the cage. Dioxygen has been implicated as the oxidant in this unusual addition of five groups to the open cage. Two silver ions connected to each other by a short argentophillic interaction reside at the core of the centrosymmetric dimer. The reaction of silver nitrate with MMK-9 yields the crystalline polymer, [{MMK9(OCH3)5Ag(AgOCH3)}2•H2O]n. This polymer consists of dimeric {MMK-9(OCH3)5Ag}2 units that are connected into strands through silver ions, which are chelated by the amine functions of one open cage and bound in η2-fashion to a pair of carbon atoms on an adjacent open cage.

INTRODUCTION The curved outer surface of fullerenes with its array of pentagons and hexagons has attracted attention ever since the initial discovery of C60.1 Once C60 was isolated as a solid,2 the reactivity of its outer surface was explored and various adducts have found to be useful in areas extending from solar energy collection and storage to medical applications. 3,4,5 The closed interior space of this highly symmetrical molecule has also fascinated chemists. Indeed, almost immediately after C60 was discovered, and before it was available in solid form, endohedral fullerenes with lanthanum ions on the inside such as La@C60 and La2C60 were detected in gas phase studies. 6 Endohedral metallofullerenes have also been obtained in soluble solid form7 and have been considered for use as magnetic resonance contrast agents and in nuclear medical applications.8,9,10 When C60 is prepared using the usual electrical arc method in a low-pressure helium atmosphere, small amounts of the endohedral He@C60 are also produced. 11 By opening a hole in a fullerene cage, it is possible to allow chemical access to the interior of the molecule. A number of such open-cage fullerenes have been synthesized. The first open-cage fullerene with one σ-bond removed was synthesized in a reaction between C60 and diazomethane by Wudl and his co-workers in 1992. 12 Later, in 1995, Wudl and Prato reported that MEMsubstituted ketolactam derivatives of C60 underwent photooxygenation of the cage to produce a 10-membered ring opening in the cage.13 Subsequently, there have also been reports on manipulating the size of the opening, starting with smaller openings and expanding the orifice size to 12-, 13-, 15- and even 19membered ring openings. 14 In a tour de force of synthetic chemistry, holes have been opened in C60, dihydrogen or water inserted into the open cage under pressure, and then the opening has been repaired to form macroscopic quantities of H2@C60 and [email protected],16 Open-cage fullerenes also have the potential to bind metal ions and to serve as precursors for the chemical synthesis of new endohedral metallofullerenes. Many of the orifices in open-cage

fullerenes are lined with Lewis base functionalities that should facilitate coordination of various metal ions. Although open-cage fullerenes have been considered as potential ligands,17,18,19 little work in this area has actually been accomplished. In 1996, Rubin and coworkers reported the first example of an adduct formed by insertion of a cobalt atom into one pentagon ring of the open-cage bisfulleroid C64H4.20 In that report, a C-C bond on the rim goes through an oxidative addition and ruptures to facilitate orifice expansion and carbon coordination to cobalt and results in the formation of CpCo(η4-C64H4). Triosmium carbonyl clusters show a similar chemistry by oxidative insertion of one of the osmium atoms into a five-membered ring of fullerene, leading to an annulene architecture.21 Despite great potentials of open-cage fullerenes, so far there are no reports on supramolecular structures (dimers or polymers) of these molecules with metals. Here we examine the reactions of silver ions with the open cage fullerene MMK-9.22 (We use the authors’ initials followed by the number used in reference 21 to designate the compounds used here.) MMK-9 has been prepared by the route shown in Scheme 1. The structure of the precursor MMK-5 was determined through spectroscopic and crystallographic studies, while MMK9 was examined only by spectroscopic means. The formation of MMK-9 was accompanied by the production of two other compounds, one an isomer of MMK-9, but MMK-9 was the major product. Previous studies of this molecule have monitored the incorporation of an H2/HD mixture into MMK-9 by 1H NMR spectroscopy23 and have examined its reaction with Ru3(CO)12. 24,25 The reaction with Ru3(CO)12 is complex and involves coordination of ruthenium atoms to the oxygen atoms of MMK-9 as well as the formation of a C-C bond between the adjacent carbon atoms to reduce the size of the orifice. Additionally, reactions that lead to the expansion of the opening in MMK-9 have been examined.26,27 In this report we structurally characterize MMK-9 as well as two open cage adducts with silver salts.

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Ph N Py

N N

Ph

+

py = 2-pyridyl Fullerene C60

180 °C, 17 h ODCB

Ph Py

N

N

Ph

N O

O

1O 2

MMK-5

MMK-9

Scheme 1. The formation of the open cage MMK-9.

RESULTS AND DISCUSSION Structural Characterization of the Open Cage Adduct, MMK9. A sample of MMK-9 was prepared as shown in Scheme 1 by a previously described method.21 Brown plates of MMK9•2.5(C6H6) were obtained by slow evaporation of a benzene solution of the compound. The structure of MMK-9 as determined by single-crystal X-ray diffraction is shown in Figure 1. There is a 12-membered ring that surrounds the opening in the formed fullerene cage. The O1-C4 and O2-C9 bond distances (1.214(4) Å and 1.201(4) Å, respectively) are indicative of the presence of keto groups. The bond that once existed in MMK-5 between C4 and C9 has broken and the resulting non-bonded C4…C9 distance is 3.130(5) Å in MMK-9. Despite the size of the orifice with 12 atoms on the rim, the space-filling diagrams in Figure 2 show little access to the interior space of the cage. Individual molecules of MMK-9 are chiral. However, MMK9•2.5(C6H6) crystallizes in a centrosymmetric space group. Consequently, an individual crystal contains a racemate.

Figure 1. Structure of the oxygenated open-cage fullerene MMK-9 with thermal ellipsoids at 50% probability. The solvent molecules are omitted for clarity.

Figure 2. Two space-filling views of MMK-9 looking down the orifice. Color codes: carbon, gray; nitrogen, blue; oxygen, red and hydrogen, white. Solvent molecules are not shown for clarity. Formation and Structure of the Dimer, {MMK9(OCH3)5Ag(AgO2CCF3)}2. When a solution of silver trifluoroacetate in methanol was layered over a solution of MMK-9 in dichloromethane black crystals of {MMK9(OCH3)5Ag(AgO2CCF3)}2•4CH2Cl2 formed at the interface of the solutions. These black crystals are insoluable in common organic solvents or water. The structure of the product has been determined by single-crystal X-ray diffraction. The asymmetric unit contains one molecule of MMK-9 with five methoxy groups attached to it, two Ag+ cations and one trifluoroacetate anion. The dimer is formed by inversion of this unit through a crystallographic center of symmetry. In the asymmetric unit, there are also one fully ordered and fully occupied dichloromethane molecule, another dichloromethane molecule that is ordered but has a half occupancy and a dichloromethane molecule with half an occupancy, which is disordered over two positions (25%:25%). The structure of the entire centrosymmetric dimer is shown in Figure 3. There are several interesting features in this structure. At the center there are two silver ions (Ag1 and its symmetry generated counterpart Ag1’) in close proximity. The Ag1-Ag1’ distance is 2.8368(12) Å. This distance is indicative of an argentophilic interaction between the two ions and is at the short end of Ag-Ag distances for such interactions.28


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Table 1. Selected Bond 9(OCH3)5Ag(AgO2CCF3)}2 9(OCH3)5Ag(AgOCH3)}2•H2O]n

{MMK[{MMK-

Dimera

Polymer Ab

Distance

Polymer Bb

2.8368(12)

2.8628(16)

Ag3…Ag3’

2.8526(18)

Ag1-C24

2.383(8)

2.431(9)

Ag3-C109

2.353(9)

Ag1-C25

2.591(8)

2.582(9)

Ag3-C110

2.585(10)

Ag1-O4

2.718(x)

2.696(x)

Ag3-O11

2.749(x)

Ag1-O5

2.633(x)

2.645(x)

Ag3-O12

2.687(x)

Ag1’-C23

2.462(8)

2.427(10)

Ag3’-C108

2.471(10)

Ag1’-O6

2.460(5)

2.524(7)

Ag3’-O13

2.497(8)

Ag1’-O7

2.501(6)

2.494(6)

Ag3’-O14

2.460(7)

Ag2-N1

2.350(8)

2.326(10)

Ag4-N3

2.373(12)

Ag2-N2

2.295(7)

2.458(8)

Ag4-N4

2.420(9)

Ag2-O9

2.200(8)

2.509(11)

Distance Ag1…Ag1’

Figure 3. Structure of the dimer {MMK9(OCH3)5Ag(AgO2CCF3)}2. Thermal contours are drawn at the 50% probability level.

Distances in Dimeric and Polymeric

Ag2-O15A

2.490(19)

Ag2-C37

2.509(11)

Ag4-C122

2.521(11)

Ag2-C53

2.344(10)

Ag4-C138

2.345(12)

[a] Dimer = {MMK-9(OCH3)5Ag(AgO2CCF3)}2. [b] Polymer = [{MMK9(OCH3)5Ag(AgOCH3)}2•H2O]n.

(A)

(B) Figure 4. (A) A view of one of the open cages in {MMK9(OCH3)5Ag(AgO2CCF3)}2 that shows how the five MeO units are distributed around one pentagon. (B) A similar view of the open cage adduct with the silver ion interactions added. Thermal contours are drawn at the 50% probability.

The Nature of the Silver Ion Mediated MeO Addition Process. The addition of five MeO units to MMK-9 involves an oxidative process as seen in Scheme 2. (This scheme is drawn to emphasize the formation of the anion MMK-9(OCH3)5-, which coordinates silver ion in the products reported here. The proton generated in Scheme 2 is likely to be taken up by the amine sites in the ureacted MMK-9 present in the reaction medium.) The pattern of MeO addition seen here is similar to arrangement of addends found by Nakamura and co-workers in the formation of C60Ph5H through the reaction of PhMgBr and Me2SCuBr with C60 (vide infra).29,30 Crystals of {MMK-9(OCH3)5Ag(AgO2CCF3)}2•4CH2Cl2 were grown under ambient conditions in the presence of methanol. The same compound is formed when MMK-9 is dissolved in benzene, toluene or chloroform instead of dichloromethane and layered by silver trifluoroacetate in methanol. No crystals formed when the silver trifluoroacetate solution was prepared in other solvents, including ethanol and 1-propanol. There was no evidence of the formation of metallic silver during the MeO addition. Thus, while silver ion may act as catalyst in this transformation, it is not the ultimate oxidant in the reaction. Significantly, no crystals formed when we performed the identical crystallization process under a dinitrogen atmosphere in the glove box with dry solvents. This observation implicates dioxygen as the oxidant in the formation of {MMK-9(OCH3)5Ag(AgO2CCF3)}2•4CH2Cl2.



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N

in Figure 4B. In both the dimer and the polymer, five MeO units have been added to the open cage in a similar fashion. In both

N N O

N O

(A)

O

O OMe MeO

5 MeOH + O2

OMe

Ag+

-

MeO

+ 2H2O + H+

MeO

MMK-9(OMe)5-

MMK-9

Scheme 2. The silver-mediated addition of MeO groups to MMK-9. There is little precedent for the reaction shown in Scheme 2. We could find only one related reaction that involved silver ion. That reaction involved the addition of two MeO units across a double bond in a di-metallo macrocycle as shown in Scheme 3.31 Additionally, the photochemical reaction of C60 with methanol in the presence acetylglycine was reported to form the diadduct, C60(OMe)2.32 Alkoxy adducts of C60 have also been obtained via substitution reactions of C60Cl6.33 R N N R

R

R

N

N N R

R

R

R

Ag

N

MeOH

N Pd

R

(B)

N

AgOTF NaOAC R is C6F5

N Pd

N

R

Ag N

MeO

OMe N

R

R

Scheme 3. The silver-mediated addition of MeO groups to a dimetallomacrocycle (see ref. 28).

We have also examined the possibility that silver(I) salts might

promote a similar addition reaction with pristine C60. However, we found no evidence of an addition reaction between C60 in benzene solution with silver trifluroracetate in methanol. This lack of reactivity may come from a need to have Lewis base sites available to coordinate to the silver ion during the addition process. Note that MMK-9 has two oxygen atoms immediately adjacent to the site of addition, and these two basic sites may be transiently involved in silver ion coordination during the addition process. We did find that using different silver counterions altered the nature of the product obtained from the reaction of methanol solutions of silver salts with MMK-9, as documented in the next section. Preparation and Structure of the Polymer, [{MMK9(OCH3)5Ag(AgOCH3)}2•H2O]n. When a solution of MMK-9 in dichloromethane was layered with a solution of silver nitrate in methanol, black plates of [{MMK9(OCH3)5Ag(AgOCH3)}2•H2O]n formed at the interface of the solutions. These crystals, like those of the dimer are insoluble in organic solvents. The asymmetric unit for this compound consists of two MMK-9(OCH3)5Ag units, which dimerize in a very similar fashion to the situation in dimeric {MMK9(OCH3)5Ag(AgO2CCF3)}2•4CH2Cl2. The two independent MMK-9(OCH3)5Ag units and the adjacent silver ions are shown in Figure 5. These two entities are similar to the corresponding portion of the dimer {MMK-9(OCH3)5Ag(AgO2CCF3)}2 shown

Figure 5. Views of the independent {MMK-9(OCH3)5 units and the silver ions attached to them in the polymer [{MMK9(OCH3)5Ag(AgOCH3)}2•H2O]n. Thermal contours are drawn at the 50% probability. compounds, two silver ions are nestled near the five-membered ring that is surrounded by five MeO groups. The major difference in the polymer when compared to the dimer is the bonding about the silver ions (Ag2 and Ag4) that arechelated by two nitrogen atoms. In the dimer, that silver ion (Ag2) has trigonal planar coordination with a trifluoroacetate ion providing the third ligand. However, in the polymer, Ag2 and Ag4 are coordinated to an adjacent open cage molecule through asymmetric η2-coordination. It is this new η2-coordination of silver to the neighboring open cage that allows the polymeric chain to propagate. Additionally, Ag2 is loosely coordinated by a methoxide ligand, but there is no corresponding methoxide bound to Ag4. The corresponding methoxide ion is located further


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away. Moreover, the methoxide ion bound to Ag2 is disordered over two sites, but only one of these is shown in Figure 5. The units shown in Figure 5 dimerize by reflection through a center of symmetry and propagate through the coordination environment of Ag2 or Ag4. Figure 6 shows a view of one polymeric chain formed from the fragment shown in Figure 5A. A second, different chain is obtained by propagation of the unit shown in Figure 5B.

shown in Figure 4(A) and Scheme 2. This addition pattern is analogous to that observed in organocuprate addition of alkyl or phenyl groups to C60 or C70.27,26,34 Such addition reactions have produced a number of interesting new fullerene adducts, including buckyferrocene, (η5-C5H5)Fe(η2-Me5C60.35 We anticipate that we will be able to utilize the facile addition of MeO units to MMK-9, and hopefully other open-cage fullerenes as well as empty cage fullerenes, to enrich the variety of fullerene compounds available.

Figure 7. A drawing showing the relationship between the two polymeric chains (one colored red, the other blue) in [{MMK9(OCH3)5Ag(AgOCH3)}2•H2O]n.

EXPERIMENTAL SECTION Synthesis of {(MMK-9)(OCH3)5Ag(AgO2CCF3)}2•4CH2Cl2. A saturated solution of 1.5 mg (0.0014 mmol) of MMK-9 in 1.2 mL dichloromethane was added to a 6 mm glass tube and layered with a saturated solution of AgO2CCF3 in methanol. After a few weeks, brown single crystals grew at the interface of the solutions. The yield was 36% based on the recovered starting material. Figure 6. A drawing of one of the polymeric strands (the one involving Ag1 and Ag2) in [{MMK9(OCH3)5Ag(AgOCH3)}2•H2O]n. Thermal contours are drawn at the 50% probability level. A second similar chain is produced from the fragment containing Ag3 and Ag4. The two chains generated from the fragments in Figure 5 run parallel to each other along the a axis of the crystal as shown in Figure 7. Thus, the chains propagate perpendicular to the plane of the page so that only the ends of the chains are seen in Figure 7. As the figure shows, the chains do not pack tightly together. Rather, there is a space consisting of 20.2 % of the unit cell that is occupied by poorly defined solvate molecules that have been treated by using the program Squeeze.

CONCLUSIONS This work demonstrates that silver mediated reactions of the open cage fullerene, MMK-9, produce a dimer and a polymer, which are, to our knowledge, the first instances of forming such structures with an open cage fullerene. Remarkably, the process also involves a facile addition of five MeO units in a pattern that surrounds the pentagon immediately below the cage orifice, as

Synthesis of the Polymer, [{MMK9(OCH3)5Ag(AgOCH3)}2•H2O]n. A saturated solution of 1.5 mg (0.0014 mmol) of MMK-9 in 1.2 mL of dichloromethane was added to a 6 mm glass tube and layered with a saturated solution of AgNO3 in methanol. After standing for a few weeks, brown single crystals of the polymer formed at the interface of the solutions. The yield was 45% based on the recovered starting material. Crystal Data for the Open-Cage Fullerene MMK-9. C95H29N2O2: M = 1230.20 g/mol, brown plates, 0.309 × 0.137 × 0.044 mm, λ = 1.54178 Å (Cu Kα), monoclinic, space group P1 (no. 2), a = 10.0211(5), b = 16.2229(9), c = 16.7816(8) Å, α = 82.685(3)°, β = 85.938(3)°, γ = 76.786(3)°, V = 2631.9(2) Å3, Z = 2, T = 90(2) K, 17249 reflections measured, 8225 unique which were used in all calculations, Bruker Apex Duo; 2θmax = 127.368°; min/max transmission = 0.5943 / 0.7536 (multi-scan absorption correction applied); direct and Patterson methods solution; full-matrix least squares based on F2 (SHELXT and SHELXL-2014/7).36 , 37 The final wR(F2) was 0.1781 (all data), conventional R1 = 0.0624 computed for 8225 reflections with I > 2σ (I) using 923 parameters with 0 restraints. Crystal Data for the Dimer {(MMK9)(OCH3)5Ag(AgO2CCF3)}2•4CH2Cl2. C89H33.25Ag2Cl4F3N2O9: M = 1688.96 g/mol, brown blocks, 0.196 × 0.113 × 0.063 mm, λ = 1.54178 Å (Cu Kα), monoclinic, space group P21/c (no. 14), a =



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24.5549(12), b = 13.8358(7), c = 20.0110(9) Å, β = 109.893(2)°, V = 6392.8(5) Å3, Z = 4, T = 90(2) K, 36485 reflections measured, 11417 unique which were used in all calculations, Bruker Apex Duo; 2θmax = 136.472°; min/max transmission = 0.3972 / 0.6155 (multi-scan absorption correction applied); direct and Patterson methods solution; full-matrix least squares based on F2 (SHELXT and SHELXL-2014/7).31,32 The final wR(F2) was 0.2587 (all data), conventional R1 = 0.0964 computed for 11417 reflections with I > 2σ (I) using 1012 parameters with 12 restraints.

Crystal structure of [{MMK-9(OCH3)5Ag(AgOCH3)}2•H2O]n C172H64Ag4N4O17: M = 2889.75 g/mol, brown plate, 0.187 × 0.172 × 0.039 mm, λ = 1.54178 Å (Cu Kα), triclinic, space group P1 (no. 2), a = 11.5733(4), b = 22.8941(8), c =29.5418(9) Å, α = 71.278(2)°, β = 82.596(2)°, γ = 83.746(2)°, T = 90(2) K, V = 7332.4(4) Å3, Z = 2, 32617 reflections measured, 2θmax = 144.398°; min/max transmission = 0.5050/0.7533 (multi-scan absorption correction applied); direct and Patterson methods solution; full-matrix least squares based on F2 (SHELXT and SHELXL-2014/7).31,2 Refined as a 2-component twin; PLATON/SQUEEZE was used for solvent accessible voids.38 The final wR(F2) was 0.2466 (all data), conventional R1 = 0.0913 computed for 25438 reflections with I > 2σ(I) using 1766 parameters with 1614 restraints.

ASSOCIATED CONTENT Supporting Information. X-ray crystallographic files in CIF format for MMK-9, {(MMK-9)(OCH3)5Ag(AgO2CCF3)}2 •4CH2Cl2., and [{MMK-9(OCH3)5Ag(AgOCH3)}2•H2O]n and spectroscopic data. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

(3) Yang, Z.; Ren, J.; Zhang, Z.; Chen, X.; Guan, G.; Qiu, L.; Zhang, Y.; Peng, H. Chem. Rev. 2015, 115, 5159−5223. (4) Guenes, S.; Neugebauer, H.; Sariciftci, N. S. Chem. Rev. 2007, 107, 1324−1338. (5) Bakry, R.; Vallant, R. M.; Najam-ul-Haq, M.; Rainer, M.; Szabo, Z.; Huck, C. W.; Bonn, G. K. Int. J. Nanomedicine 2007, 2, 639–649. (6) Heath, J. R.; O’Brien, S. C.; Zhang, Q.; Liu, Y.; Curl, R. F.; Kroto, H. W.; Tittel, F. K. Smalley, R. E. J. Am. Chem. Soc. 1985, 107,1179-1180. (7) Popov, A. A.; Yang, S.-F.; Dunsch, L. Chem. Rev. 2013, 113, 5989-6113. (8) Mikawa, M.; Kato, H.; Okumura, M.; Narazaki, M.; Kanazawa, Y.; Miwa, N.; Shinohara, H. Bioconjugate Chem. 2001, 12, 510-514. (9) Toth, E.; Bolskar, R. D.; Borel, A.; Gonzalez, G.; Helm, L.; Merbach, A. E.; Sitharaman, B.; Wilson, L. J. J. Am. Chem. Soc. 2005, 127, 799-805. (10) Ghiassi, K. B.; Olmstead, M. M.; Balch, A. L. Dalton Trans. 2014, 43, 7346-7358. (11) Saunders, M.; Jimenez-Vazquez, H. A.; Cross, R. J.; Poreda, R. J. Science 1993, 259, 1428-1430. (12) Suzuki, T.; Q. Li, Q.; Khemani, K.; Wudl, F. J. Am. Chem. Soc. 1992, 114, 7301-7302. (13) Hummelen, J. C.; Prato, M.; Wudl, F. J. Am. Chem. Soc. 1995, 117, 7003-7004.

Corresponding Authors * E-mail: [email protected], [email protected]

(14) Vougioukalakis, G. C.; Roubelakis, R.; Orfanopoulos, M. Chem. Soc. Rev. 2010, 39, 817–844.

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT We thank the National Science Foundation (Grant CHE-1305125 to ALB and MMO) for support.

(15) Komatsu, K.; Murata, M.; Murata, Y. Science 2005, 307, 238-240. (16) Kurotobi, K.; Murata, Y. Science 2011, 333, 613-616. (17) Nierengarten, J.-F. Angew. Chem. Int. Ed. 2001, 40, 29732974. (18) Rubin, Y. Top. Current Chem. 1999, 199, 67-91. (19) Rubin, Y. Chem. Eur. J. 1997, 3, 1009-1016.

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